Degradation of DEET by ozonation in aqueous solution

This study was undertaken in order to understand the factors affecting the degradation of an insect repellent, N,N-diethyl-m-toluamide (DEET) by ozonation. Kinetic studies on DEET degradation were carried out under different operating conditions, such as varied ozone doses, pH values of solution, initial concentrations of DEET, and solution temperatures. The degradation of DEET by ozonation follows the pseudo-first-order kinetic model. The rate of DEET degradation increased exponentially with temperature in the range studied (20–50 °C) and in proportion with the dosage of ozone applied. The ozonation of DEET under different pH conditions in the presence of phosphate buffer occurred in two stages. During the first stage, the rate constant, kobs, increased with increasing pH, whereas in the second stage, the rate constant, kobs2, increased from pH 2.3 up to 9.9, however, it decreased when the pH value exceeded 9.9. In the case where buffers were not employed, the kobs were found to increase exponentially with pH from 2.5 to 9.2 and the ozonation was observed to occur in one stage. The rate of degradation decreased exponentially with the initial concentration of DEET.GC/MS analysis of the by-products from DEET degradation were identified to be N,N-diethyl-formamide, N,N-diethyl-4-methylpent-2-enamide, 4-methylhex-2-enedioic acid, N-ethyl-m-toluamide, N,N-diethyl-o-toluamide, N-acetyl-N-ethyl-m-toluamide, N-acetyl-N-ethyl-m-toluamide 2-(diethylamino)-1-m-tolylethanone and 2-(diethylcarbamoyl)-4-methylhex-2-enedioic acid. These by-products resulted from ozonation of the aliphatic chain as well as the aromatic ring of DEET during the degradation process.